CN100532339C - Process for producing benzal chloride or chloro benzal chloride - Google Patents
Process for producing benzal chloride or chloro benzal chloride Download PDFInfo
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- CN100532339C CN100532339C CNB2007100232460A CN200710023246A CN100532339C CN 100532339 C CN100532339 C CN 100532339C CN B2007100232460 A CNB2007100232460 A CN B2007100232460A CN 200710023246 A CN200710023246 A CN 200710023246A CN 100532339 C CN100532339 C CN 100532339C
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- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 43
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 title claims description 41
- 230000008569 process Effects 0.000 title abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 102
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 40
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000460 chlorine Substances 0.000 claims description 30
- 229910052801 chlorine Inorganic materials 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 238000000066 reactive distillation Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 241000282326 Felis catus Species 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000007306 turnover Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 230000005494 condensation Effects 0.000 description 8
- -1 phenyl aldehyde Chemical class 0.000 description 8
- BMHBMLLQKJESDS-UHFFFAOYSA-N benzene;formaldehyde Chemical class O=C.C1=CC=CC=C1 BMHBMLLQKJESDS-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 description 6
- ZBOGUDPFEVIZIQ-UHFFFAOYSA-N toluene;dihydrochloride Chemical compound Cl.Cl.CC1=CC=CC=C1 ZBOGUDPFEVIZIQ-UHFFFAOYSA-N 0.000 description 6
- DSPKXCZGSQZMRS-UHFFFAOYSA-N C(C1=CC=CC=C1)Cl.[Cl] Chemical group C(C1=CC=CC=C1)Cl.[Cl] DSPKXCZGSQZMRS-UHFFFAOYSA-N 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 4
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MFHPYLFZSCSNST-UHFFFAOYSA-N 1-chloro-2-(trichloromethyl)benzene Chemical compound ClC1=CC=CC=C1C(Cl)(Cl)Cl MFHPYLFZSCSNST-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- GKTNMSYLASANEG-UHFFFAOYSA-N ClC(C1=CC=CC=C1)=CC1=CC=CC=C1.Cl.Cl Chemical compound ClC(C1=CC=CC=C1)=CC1=CC=CC=C1.Cl.Cl GKTNMSYLASANEG-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 1
- DERZBLKQOCDDDZ-JLHYYAGUSA-N cinnarizine Chemical compound C1CN(C(C=2C=CC=CC=2)C=2C=CC=CC=2)CCN1C\C=C\C1=CC=CC=C1 DERZBLKQOCDDDZ-JLHYYAGUSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
This invention relates to a preparation method of benzal dichloro or chlor-benzal dichloro. The invention process: inlet toluene or chlorotoluene, benzyl chloride or chlor- benzyl chloride and chlorine gas according to certain mol ratio to reactor that coupled with fractionating tower or prechlorination reactor, under series stable operation condition, control the operating pressure of fractionating tower at 0.002 to 0.05MPa. The chlorination is stimulated by sunlight or blue light, temperature of reactor is controlled at 80 to 120 deg.
Description
Technical field
The present invention relates to a kind of processing method of producing benzylidene chloride or chloro benzylidene chloride, specifically, be that the method that adopts reactor and rectifying tower to be coupled uses the chlorine direct chlorination to generate benzylidene chloride in the mixture of toluene, Benzyl Chloride or toluene and Benzyl Chloride, and the method that the mixture of chlorotoluene, chloro Benzyl Chloride or chlorotoluene and chloro Benzyl Chloride is generated the chloro benzylidene chloride with the chlorine direct chlorination.
Background technology
Benzylidene chloride has another name called chloro-benzal, toluene dichloride or protochloride benzyl, is a kind of important organic synthesis intermediate of industries such as chemical industry, medicine, agricultural chemicals, can be used for producing phenyl aldehyde and styracin, Stutgin etc.Its chlorinated derivative comprises benzyl chloride fork dichloro and adjacent benzyl chloride fork dichloro, is the important intermediate of producing 4-chloro-benzaldehyde, o-chlorobenzaldehyde etc.
Benzylidene chloride and chloro benzylidene chloride are that raw material carries out the side chain chlorination production at industrial employing toluene or Benzyl Chloride, toluene(mono)chloride or chloro Benzyl Chloride, and its reaction mechanism all is a free radical reaction.Therefore, in industrial benzylidene chloride or the chloro benzylidene chloride production process, the composition of chlorated liquid generally also contains Benzyl Chloride and benzotrichloride, chloro Benzyl Chloride and chloro benzotrichloride etc. except benzylidene chloride or chloro benzylidene chloride.
Document (Chen Yongli. the research of the synthetic benzyl dichloride of chlorination toluene method.The Shaanxi chemical industry, 1996,4:31-32.) carry out Benzyl Side-Chain Chloride as light source with high voltage mercury lamp, under 120～140 ℃ of temperature of reaction, after reaction finished, the content of benzyl dichloride was 91% in the chlorated liquid.
Document (Zhu Chengjie, Wang Changqiu. chlorination toluene prepares the research of phenyl aldehyde.Huaihai Institute of Technology journal (natural science edition).1996,5 (1): 71-73.) with toluene be raw material, in still formula illumination reaction device, carry out chlorination reaction and prepare benzylidene chloride.In the presence of radical initiator, be light source with the 40W fluorescent lamp, 90 ℃ of temperature of reaction, when reaction finished, the content of benzylidene chloride reached at 70～77% o'clock in the chlorated liquid, and the content of Benzyl Chloride is 23～18%, the content of benzotrichloride is less than 5%, and content of toluene is less than 1.5%.
Document (Wang Yi, Qiao Xu. Benzyl Chloride prepares the research of phenyl aldehyde.Fine-chemical intermediate, 2005,35 (1): 44-46,49.) adopt common loop reactor, with the light source of 12W fluorescent lamp, be the raw material production benzylidene chloride with the Benzyl Chloride as initiation reaction, carry out optical chlorinating reaction at 115 ℃, when the transformation efficiency of Benzyl Chloride reaches 60.6%, the content of benzylidene chloride reaches 60.8% in the reaction solution, and the content of benzotrichloride is less than 1.8%.
(US4056455 2001-07-24) discloses a cover continuous light chlorating technical process to patent.Take the mode of 6 cascade reaction stills, and placed in-line reactor reduces successively, under temperature of reaction 75-145 ℃, carry out chlorination reaction, toluene feeds in the placed in-line reactor continuously, chlorine feeds in the reactor respectively, in order to obtain benzylidene chloride, the chlorine of feeding and the mol ratio of toluene are 2.01-2.05:1.
Document (Yang Ting. the exploration of synthetic 4-chloro-benzaldehyde reaction conditions.The Kweiyang gold is built college journal, and 2002,45 (4): 107-108.) having studied parachlorotoluene is the processing condition of raw material through phosphorus trichloride chlorination, synthetic 4-chloro-benzaldehyde of two step of tindichloride hydrolysis.Because degree of depth chlorination generates a large amount of to benzyl chloride river trichlorine, the by-product Chlorodracylic acid that hydrolysis reaction production is a large amount of, the yield of 4-chloro-benzaldehyde has only 59.2%.
By forefathers and the inventor to being raw material with toluene or toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride, synthesis of benzylidene dichloro or chloro benzylidene chloride, and further discovering of hydrolysis synthesizing benzaldehyde or chlorinated benzene formaldehyde, because the toluene or the side chain chlorination synthesis of benzylidene dichloro of toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride or the reaction of chloro benzylidene chloride are consecutive chlorination reactions, the difficult control of the chlorination degree of depth, the by-product benzotrichloride or the chloro benzotrichloride of generation are more.Need to isolate highly purified benzylidene chloride or chloro benzylidene chloride, then hydrolysis synthesizing benzaldehyde or chlorinated benzene formaldehyde through rectification under vacuum.Perhaps directly use chlorated liquid to be hydrolyzed, then generate phenyl aldehyde or chlorinated benzene formaldehyde and phenylformic acid or the benzoic mixture of chloro, behind crystallization method separate benzoic acid or chlorinated benzene formic acid, obtain phenyl aldehyde or chlorinated benzene formaldehyde products.No matter which kind of method is calculated with raw material toluene or toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride, the yield of phenyl aldehyde or chlorinated benzene formaldehyde is all not high.For this reason, part enterprise adopts the tankage that contain benzylidene chloride or chloro benzylidene chloride of by-product when producing Benzyl Chloride or chloro Benzyl Chloride to produce phenyl aldehyde or chlorinated benzene formaldehyde for the raw material hydrolysis, because the tankage amount of by-product is little, output is restricted, and quality product is relatively poor.In addition, because tankage are formed complexity, cause environmental pollution serious.Therefore, set up large-scale high-purity benzylidene chloride or chloro benzylidene chloride production technique and device, be significant for the output and the quality that promote phenyl aldehyde or chlorinated benzene formaldehyde.
Summary of the invention
The object of the present invention is to provide a kind of method that reactor and rectifying tower are coupled and produce benzylidene chloride or replace benzylidene chloride.
Purpose of the present invention can reach by following measure:
The reaction and rectification device that this method adopts mainly is made up of rectifying tower and reactor coupling, and complete assembly comprises reactive distillation district and disengaging zone, and the reactive distillation district is coupled to form by the rectification zone of reactor and rectifying tower; Raw material is toluene or toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride; Raw material feeds and first coupled reactor of rectifying tower coupled, and chlorine feeds each coupled reactor that is connected with rectifying tower continuously, and perhaps raw material feeds the prechlorination reactor, and chlorine feeds each coupled reactor and the prechlorination reactor that is connected with rectifying tower continuously; Cat head total reflux, the material of reflux exchanger enter first coupled reactor, return cat head; Return rectifying tower after material enters reactor reaction in the tower; The rectifying tower working pressure is at 0.002～0.05MPa; Chlorination reaction adopts daylight or blue light to cause, and the temperature in the reactor is at 80～120 ℃.
Described method, raw material is toluene or Benzyl Chloride when wherein producing benzylidene chloride; Raw material is toluene(mono)chloride or chloro Benzyl Chloride when producing the chloro benzylidene chloride.
Described method, wherein the mole proportioning of chlorine total amount and raw material is 0.9～2.1:1.
Described method, wherein the turnover material of coupled reactor all links to each other with rectifying tower, and coupled reactor platform number is 1～N platform (N≤10), generally below 6, preferred 3～4.
Described method, when reactor was many, chlorine fed each reactor respectively in 1～99% (generally 10～90%) ratio that accounts for total logical chlorine dose.
Described method, wherein the prechlorination reactor is arranged on the below of last coupled reactor.
Described method, wherein raw material feeds the 1st coupled reactor or prechlorination reactor continuously.
Described method, wherein rectifying tower is operated under reduced pressure, and working pressure is 0.002～0.05MPa, preferred 0.004～0.025MPa.
Described method, wherein the rectification zone stage number is the 3-20 piece, preferably at the 5-10 piece, the column plate of some amount at interval between the adjacent reactor also can be tightly adjacent.
Described method, wherein the disengaging zone stage number is at the 10-50 piece, preferred 20-30 piece.
No matter being the reactive distillation district or the form of the rectifying tower of disengaging zone, can be packing tower, also can be tray column or other types rectifying tower.Under the continous-stable operational condition, the working pressure of control rectifying tower, making tower top temperature is 90～115 ℃, column bottom temperature is 130～180 ℃.
Reactor can be the bubble tower of being made by glass both, or had the enamel of visor or the bubble tower of lining teflon.Light source can be provided by fluorescent lamp or blue-ray light, daylight or blue light fluorescent tube place the periphery of glass bubble tower, or the visor by enamel or lining teflon bubble tower is to the tower internal radiation, or places the quartz glass sleeve of enamel or lining teflon bubble tower inside.80～120 ℃ of control reaction temperature are preferably between 100～105 ℃, and the chlorine of feeding can generate benzylidene chloride or chloro benzylidene chloride with toluene or toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride generation chlorination reaction.
The raw material of preparation benzylidene chloride or chloro benzylidene chloride can be toluene or toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride, raw material can feed and first coupled reactor of rectifying tower coupled, perhaps feed a prechlorination reactor, prechlorination to the molar fraction of benzylidene chloride or chloro benzylidene chloride is 25～35%, from the column plate charging of N platform and rectifying tower coupled coupled reactor below.The massfraction that keeps benzylidene chloride in the chlorination reactor or chloro benzylidene chloride is 1～30%, and the massfraction of benzylidene chloride or chloro benzylidene chloride increases successively in downward each chlorination reactor of cat head chlorination reactor.The tower still begins continuous discharging simultaneously, regulates flow and makes the liquid level of tower still remain unchanged.The massfraction of benzylidene chloride or chloro benzylidene chloride can reach more than 99% in the material that the tower still comes out, and the massfraction of Benzyl Chloride or chloro Benzyl Chloride is lower than 0.5%, and the massfraction of benzotrichloride or chloro benzotrichloride is lower than 0.5%.
Advantage of the present invention is:
The present invention places the outside of rectifying tower, the material in the reactor to come from the column plate of its top reactor, enters the column plate of its below after reaction, not only connects each other but also separate between reactor and the rectifying tower.This coupled modes both can keep the advantage of reactive distillation integrated technology, can make reactor operating condition and rectifying tower operational condition keep independent simultaneously again.Reactor operating condition and rectifying tower operational condition can be inconsistent, and reactor volume can freely adjust, and realized the optimum matching of response capacity and separating power.For the chlorination reaction of synthesis of benzylidene dichloro or chloro benzylidene chloride, chlorination reaction temperature is between 80～120 ℃, and reaction pressure is a normal pressure.And the boiling point height of benzylidene chloride or chloro benzylidene chloride, distillation operation pressure is negative pressure.Reactor and rectifying tower coupled mode that the present invention adopts, preparation benzylidene chloride or chloro benzylidene chloride can be coupled normal pressure chlorination reaction and rectification under vacuum, not only reach the effect of high conversion, highly selective productive target product, and the volume of reactor and reacting weight can be regulated arbitrarily, technical process is short, and operation control is flexible, and production cost is low, the economic benefit height helps realizing large-scale industrial production.
Description of drawings
Fig. 1 is the process flow sheet that benzylidene chloride or chloro benzylidene chloride are produced in reactor and rectifying tower coupling.Earlier Benzyl Chloride or chloro Benzyl Chloride are joined and carry out chlorination in the reactor, make the 1st in the reaction of reactor to the N platform benzylidene chloride or the molar fraction of chloro benzylidene chloride increase successively in 10%～30% scope.Feed Benzyl Chloride or chloro Benzyl Chloride and chlorine continuously to reactor then, open the rectifying tower vacuum system.When at the bottom of the rectifying Tata material being arranged, open the reboiler heating, open the water coolant of complete condenser.Material in the tower still is vaporized and enter the 1st reactor chlorination to overhead condensation, and chlorination reaction liquid returns the uppermost column plate of rectifying tower.The liquid phase material of rectifying tower enters be attached thereto the 2nd respectively to N platform reactor from the column plate extraction, through separating entering rectifying tower from corresponding next piece column plate after the chlorination reaction.After the reaction solution that N platform reactor comes out entered rectifying tower, the stripping section in the tower bottom further separated, and obtained highly purified benzylidene chloride or chloro benzylidene chloride at the bottom of tower, and from the continuous discharging of tower still.Chlorination reaction adopts daylight or blue light to cause.
Fig. 2 has the reactor of prechlorination reactor and the process flow sheet that benzylidene chloride or chloro benzylidene chloride are produced in the rectifying tower coupling.Earlier toluene or toluene(mono)chloride compound are joined the prechlorination reactor and with rectifying tower coupled reactor in carry out prechlorination, making the molar fraction of benzylidene chloride in the prechlorination reactor or chloro benzylidene chloride is 25～35%, increases successively in 10%～30% scope with the benzylidene chloride in the 1st reactor to the N platform reaction of rectifying tower coupled or the molar fraction of chloro benzylidene chloride.Feed toluene or toluene(mono)chloride continuously to the prechlorination reactor then, feed chlorine continuously, open the rectifying tower vacuum system to all reactors.When at the bottom of the rectifying Tata material being arranged, open the reboiler heating, open the water coolant of complete condenser.Material in the tower still is vaporized and enter the 1st reactor chlorination to overhead condensation, and chlorination reaction liquid returns the uppermost column plate of rectifying tower.The liquid phase material of rectifying tower enters be attached thereto the 2nd respectively to N platform reactor from the column plate extraction, through separating entering rectifying tower from corresponding next piece column plate after the chlorination reaction.The reaction solution that N platform reactor comes out enters rectifying tower, and the stripping section in the tower bottom further separates, and obtains highly purified benzylidene chloride or chloro benzylidene chloride at the bottom of tower, and from the continuous discharging of tower still.Chlorination reaction adopts daylight or blue light to cause.
Embodiment
For further specifying the present invention, be illustrated below by embodiment:
Embodiment 1:
Adopt technical process as shown in Figure 1, with rectifying tower coupled reactor number be 3.Benzyl Chloride and chlorine feed are 1.4kmol/h, and the allocation proportion of chlorine in 3 reactors is: 0.45:0.32:0.23, and the overhead condensation amount is 1000L/h, the chlorination reaction actuator temperature is 95 ℃, rectifying tower working pressure 0.025MPa, the rectification zone stage number is 9, the disengaging zone stage number is 30.Behind reactive distillation, the mole of tower still consists of: Benzyl Chloride 0.1%, benzylidene chloride 99.4%, benzotrichloride 0.45%, ring toluene dichloride 0.05%.
Embodiment 2:
Adopt technical process as shown in Figure 2, a prechlorination reactor, with rectifying tower coupled reactor number be 3.Toluene feed is 1.4kmol/h, chlorine feed is 2.8kmol/h, the allocation proportion of chlorine in 4 reactors is 0.65:0.15:0.1:0.1, the overhead condensation amount is 1000L/h, the chlorination reaction actuator temperature is 80 ℃, rectifying tower working pressure 0.05MPa, the rectification zone stage number is 6, the disengaging zone stage number is 25.Behind reactive distillation, the mole of tower still consists of: Benzyl Chloride 0.2%, benzylidene chloride 99.1%, benzotrichloride 0.55%, ring toluene dichloride 0.05%.
Embodiment 3:
Adopt technical process as shown in Figure 1, with rectifying tower coupled reactor number be 3.Adjacent chlorine Benzyl Chloride and chlorine are 1.4kmol/h, and the allocation proportion of chlorine in 3 reactors is: 0.5:0.3:0.2, and the overhead condensation amount is 1300L/h, the chlorination reaction actuator temperature is 120 ℃, rectifying tower working pressure 0.002MPa, the rectification zone stage number is 6, the disengaging zone stage number is 20.Behind reactive distillation, the mole of tower still consists of: adjacent chlorine Benzyl Chloride 0.15%, adjacent benzyl chloride fork dichloro 99.15%, adjacent benzyl chloride river trichlorine 0.55%, ring toluene dichloride 0.15%.
Embodiment 4:
Adopt technical process as shown in Figure 2, a prechlorination reactor, with rectifying tower coupled reactor number be 3.The ortho-chlorotolu'ene charging is 1.4kmol/h, chlorine feed is 2.8kmol/h, the allocation proportion of chlorine in 4 reactors is 0.65:0.15:0.1:0.1, the overhead condensation amount is 1000L/h, the chlorination reaction actuator temperature is 80 ℃, rectifying tower working pressure 0.05MPa, the rectification zone stage number is 8, the disengaging zone stage number is 26.Behind reactive distillation, the mole of tower still consists of: adjacent chlorine Benzyl Chloride 0.2%, adjacent benzyl chloride fork dichloro 99.15%, adjacent benzyl chloride river trichlorine 0.5%, ring toluene dichloride 0.05%.
Embodiment 5:
Adopt technical process as shown in Figure 1, with rectifying tower coupled reactor number be 3.Chlorine Benzyl Chloride and chlorine feed are 1.4kmol/h, and the allocation proportion of chlorine in 3 reactors is: 0.5:0.3:0.2, and the overhead condensation amount is 1300L/h, the chlorination reaction actuator temperature is 120 ℃, rectifying tower working pressure 0.002MPa, the rectification zone stage number is 6, the disengaging zone stage number is 26.Behind reactive distillation, the mole of tower still consists of: to chlorine Benzyl Chloride 0.15%, and to benzyl chloride fork dichloro 99.15%, to benzyl chloride river trichlorine 0.55%, ring toluene dichloride 0.15%.
Embodiment 6:
Adopt technical process as shown in Figure 2, a prechlorination reactor, with rectifying tower coupled reactor number be 3.The parachlorotoluene charging is 1.4kmol/h, chlorine feed is 2.8kmol/h, the allocation proportion of chlorine in 4 reactors is: 0.65:0.15:0.1:0.1, the overhead condensation amount is 1300L/h, the chlorination reaction actuator temperature is 105 ℃, rectifying tower working pressure 0.001MPa, the rectification zone stage number is 8, the disengaging zone stage number is 30.Behind reactive distillation, the mole of tower still consists of: to chlorine Benzyl Chloride 0.2%, and to benzyl chloride fork dichloro 99.2%, to benzyl chloride river trichlorine 0.45%, ring toluene dichloride 0.05%.
Claims (13)
1, the method for a kind of reactor and rectifying tower coupling production benzylidene chloride or chloro benzylidene chloride, the reaction and rectification device that it is characterized in that this method employing mainly is made up of rectifying tower and reactor coupling, complete assembly comprises reactive distillation district and disengaging zone, and the reactive distillation district is coupled to form by the rectification zone of reactor and rectifying tower; Raw material is toluene or toluene(mono)chloride, Benzyl Chloride or chloro Benzyl Chloride; Raw material feeds and first coupled reactor of rectifying tower coupled, and chlorine feeds each coupled reactor that is connected with rectifying tower continuously, and perhaps raw material feeds the prechlorination reactor, and chlorine feeds each coupled reactor and the prechlorination reactor that is connected with rectifying tower continuously; Cat head total reflux, the material of reflux exchanger enter first coupled reactor, return cat head; Return rectifying tower after material enters reactor reaction in the tower; Prechlorination to the molar fraction of benzylidene chloride or chloro benzylidene chloride is 25～35%; The massfraction that keeps benzylidene chloride in the chlorination reactor or chloro benzylidene chloride is 1～30%, and the massfraction of benzylidene chloride or chloro benzylidene chloride increases successively in downward each chlorination reactor of cat head chlorination reactor; The rectifying tower working pressure is at 0.002～0.05MPa; Chlorination reaction adopts daylight or blue light to cause, and the temperature in the reactor is at 80～120 ℃.
2, method according to claim 1, raw material is toluene or Benzyl Chloride when it is characterized in that producing benzylidene chloride; Raw material is toluene(mono)chloride or chloro Benzyl Chloride when producing the chloro benzylidene chloride.
3, method according to claim 1, the mole proportioning that it is characterized in that chlorine total amount and raw material is 0.9～2.1:1.
4, method according to claim 1 is characterized in that the turnover material of coupled reactor all links to each other with rectifying tower, and coupled reactor platform number is 1～10.
5, method according to claim 4 is characterized in that the turnover material of coupled reactor all links to each other with rectifying tower, and coupled reactor platform number is 3～4.
According to claim 4 or 5 described methods, it is characterized in that when reactor is many that 6, chlorine feeds each reactor respectively in 1～99% ratio that accounts for total logical chlorine dose.
7, method according to claim 1, it is characterized in that the prechlorination reactor be arranged on last coupled reactor below.
8, method according to claim 1 is characterized in that raw material feeds first coupled reactor or prechlorination reactor continuously.
9, method according to claim 1, the working pressure that it is characterized in that rectifying tower is 0.004～0.025MPa.
10, method according to claim 1 is characterized in that the rectification zone stage number is the 3-20 piece.
11, method according to claim 10 is characterized in that the rectification zone stage number is the 5-10 piece.
12, method according to claim 1 is characterized in that the disengaging zone stage number is the 10-50 piece.
13, method according to claim 12 is characterized in that the disengaging zone stage number is the 20-30 piece.
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| CN102320943B (en) * | 2011-08-03 | 2014-02-19 | 浙江云涛生物技术股份有限公司 | Preparation method of benzaldehyde |
| CN102285863A (en) * | 2011-08-03 | 2011-12-21 | 朱运涛 | Method for preparing benzal chloride |
| CN108409528A (en) * | 2018-01-31 | 2018-08-17 | 青岛和兴精细化学有限公司 | A kind of new process prepared using novel reaction equipment to benzyl dichloride |
| CN109020801B (en) * | 2018-09-04 | 2020-11-06 | 江苏超跃化学有限公司 | Method for recovering p-chlorobenzoic acid as byproduct in p-chlorobenzaldehyde production process |
| CN111620813B (en) * | 2020-07-07 | 2023-08-01 | 天津科技大学 | Method for continuously chloridizing and synthesizing tetrachloropyridine |
| CN111825520A (en) * | 2020-07-27 | 2020-10-27 | 西安思科赛实业有限公司 | Preparation process of alpha, alpha' -tetrachloro-o-xylene |
| CN113233954B (en) * | 2021-04-30 | 2023-07-07 | 新乡瑞诚科技股份有限公司 | Method for improving selectivity of chlorination reaction process |
| CN113896615B (en) * | 2021-11-18 | 2023-08-11 | 常州新东化工发展有限公司 | Method for adsorbing and purifying impurities by using high-purity benzyl chloride |
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| US4056455A (en) * | 1975-07-05 | 1977-11-01 | Hoechst Aktiengesellschaft | Process for the continuous preparation of mono- or di-(trichloromethyl)-benzenes |
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